Polyloxy alkylene sulfides

ABSTRACT

Compounds of the formula   WHEREIN R is an alkyl or aralkyl group; each n is an integer of from five to 50; A is a sulfide, sulfoxide or sulfone group; R1 is hydrogen or a lower alkyl group; and Ro is a halophenyl group, an alkyl or aralkyl group, halophenylethyl or halobenzyl group, or a group of the formula   WHEREIN R, R1 and n are defined above. These compositions have surfactant and/or biological utilities.

United States Patent [72] inventors Richard A. Hickner; 3,174,900 3/I965 Wyant 260/609 Howard L. Young, both of Midland, Mich. 3,288,858 Il/ l 966 Lyness el al. 260/607 [21] Appl. No. 751,371 3,346,504 l0/l967Herrmann 260/607 UX 5253 3: Primary Examiner-Joseph P. Brust 73 AssigneeThe Dow Chemical Company gf 'gz'g' z'f't J R L M i d Midland, Mich.ltorneysnswo ur m an ames oc ea Continuation-impart oi application Ser.No.

573,500, s- 1 1966, n n ned- ABSTRACT: Compounds of the formula Thisapplication Aug. 9, 1968, Ser. No. R0 cH,oH,o CH-CH -[Al-Ro 1 [54]POLYLOXY ALKYLENE SULFIDES 9 Claims, No Drawings wherein R is an alkylor aralkyl group; each n is an integer of from five to 50; A is asulfide, sulfoxide or sulfone group; R is [52] cl hydrogen or a loweralkyl group; and R, is a halophenyl group, [5 n In Cl Con an alkyl oraralkyl group halophenylethyl or halobenzyl 149/14 g p or g QLELEP ofthe formLla r n V M [50] Field oi Search 260/607 A.

609 A. 609 F; 252/161 R-O-{CH OIhO} JHCH,-

so 1 Relerences Cited UNlTED STATES PATENTS wherein R, R, and n aredefined above. These compositions 2 864 866 12/1958 Louihan 260/607 havesu'facam md/m bilgical 3,135,804 6/1964 Von Brachel et al. 260/609 1POLYLOXY ALKYLENE suunnas CROSS-REFERENCE TO RELATED APPLICATION SUMMARYOF THE INVENTION This invention relates to novel compositions of matterhaving useful surfactant and/or biological properties and to methods ofpreparing such compositions. More particularly, the present inventionrelates to aromatic or alkyl sulfur-containing polyoxyalkylenesurfactant compounds with low foam characteristics, some of which arevery active for the control of certain specific insect pests, forpreventing the growth of particular strains of fungi, in the control ofmites and as anthelmintics.

The condensation of a beta-hydroxyethyl sulfide with a compoundcontaining a hydroxyl group is a known reaction. Broad classes ofdiverse reaction products (useful primarily as synthetic lubricants)have been prepared by means of this reaction, as disclosed, for example,in US. Pat. No. 2,582,605 to Richter et al. Classes of sulfone compoundswhich contain polyoxyalkylene groups are also known (US. Pat. No.2,378,55l to Hentrich et al. and US. Pat. No. 2,474,808 to Schoene).

The compounds of the present invention may be represented by the formulawherein R is an alkyl groupof from to [8 carbon atoms or an alkyl phenylgroup of from l4 to 24 carbon atoms, n is an integer of from five to 50,-A is a divalent sulfur, sulfoxide or sulfone group 0 (S-, S or S R ishydrogen or an alkyl group of from one to four carbon atoms,'and R is ahalophenyl group, an alkyl group of from one to 12 carbon atoms(preferably three to eight carbon atoms), an aryl-containing hydrocarbongroup. preferably monocyclic, of no more than carbon atoms (such as aphenyl, 0-, mor p-cumenyl, B-naphthyl, tolyl, xylyl, duryl, phenethyl ora benzyl group), a halophenylethyl group (such as p-chlorophenethyl), ahalobenzyl group (such as 0-, mor p-bromobenzyl), or a group of theformula nO-R ll l

wherein X is a halogen (Cl, Br, F or I); R is as defined above and ispreferably a straight chain alkyl group of from l2 to lo carbon atoms,or an alkylphenyl group of 14 to 18 carbon atoms, said alkyl groups oralkyl substituents being, for instance, lower alkyl groups of from oneto four carbon atoms, a straight or branched chain pentyl, hexyl, octyl,nonyl, decyl, undecyl or dodecyl group, and n is as defined above andpreferably from nine to 50, more preferably lS-40.

The initial condensation reaction (1) (a) or (2) (a) is carried out inthe presence of an acid catalyst, preferably using an oxyalkylatedalkylphenol wherein the alkyl substituent on the benzene ring is abranched chain alkyl group of from eight to 12 carbon atoms or anoxyalkylated alcohol containing ID to 18 carbon atoms in the alcoholmoiety. The water produced by the condensation reaction may be removedby azeotropic distillation or by other conventional means. Typicalcatalysts which may be used for the condensation steps of reactions l(a) and (2) (a) include para-toluene sulfonic acid, phosphoric acid andsulfonated ion exchange resins (based on styrene divinylbenzenecopolymer). The condensation product may be oxidized to the sulfoxideand/or sulfone in situ according to reactions (l)(b), (c) and (2)(b),(c) or the product may be separated and purified prior to oxidation. Anyconventional oxidizing agent which does not cleave the molecule may beused to form the sulfoxide and sulfone products. Aqueous hydrogenperoxide has been found to be very suitable for this purpose. To formthe sulfoxide products, the sulfides are treated with the theoreticalamount of 30 percent hydrogen peroxide in acetone or acetic acid at roomtemperature. The sulfones may be prepared by oxidizing either thesulfides or sulfoxides atelevated temperature (above room temperature)with an excess of pero iride in acetic acid or with potassiumpermanganate.

Reaction (3 )(a) is ordinarily carried out in the presence of a base ofan acid acceptor. The reaction can also be carried out with a mercaptansalt such as NaSR or KSR wherein R is as previously defined. Theresulting sulfide product is then oxidized in the same manner as inreactions (l)(b), (c) and (2)(b), (c) to the corresponding sulfoxidesand/or sulfones.

The halogenated starting materials of reaction (3) may be SPECIFICEMBODIMENTS Typical reactions include the following:

( ams)- 30 percent aqueous l H20:

O CHZCHQO II O oomcmo omcms CHzCHz-Q-Jir jaw omcmoi cmsm CH3 l HH-Mixture derived from the polymerization of ethylene.

The compounds produced according to the present invention exhibitsurprising low-foam surfactant properties. This is unusual in view ofthe fact the unmodified ethoxylated alkylphenols and alcohols arehigh-foaming surfactants XAMPLES. V. D) to the sulfoxide was carried outby the dropwise addition of 30 percent aqueous hydrogen peroxide to thesulfide at temperatures of from room temperature to about 60 C. The

Furthermore, many of the compounds (as well as mixtures of 5 amounts ofreactants used for the oxidation are given in table such compounds)produced according to the invention are ac- I. tive fungicides,acaricides and anthelmintics. Surfactants with low foamingcharacteristics are particularly desirable for use GENERAL METHOD C magncultural Sprays and m latex P formulatfonsof lo Oxidation of thesulfide (or sulfoxide) from either General t the compounds which have achlorophenyl substltuent have Method A B or D to the sulfone was carriedout by the been found) be anthelmmtic a m wise addition of 30 percentaqueous hydrogen peroxide to either the sulfide or sulfoxide attemperatures of from to GENERAL METHOD A 60 C. The amounts of reactantsand yields obtained are given Is in table 1. Peracetic acid was alsoused to prepare the sulfones. 1 H R08 011.0110};

\ A 1|a GENERAL METHOD D r- NwH R-o oH.omo -o1wmem "T 1 m n 1 20 R- O-CH2CH:O CHCHaSRo 1120 NaCl ln thls reactlon, the values of n and thesubstltuents A represented by R and R are given in table I. along withthe 1 amounts f reactants i and i z th I t d To a 0.1 mole sample of themercaptan (R Sl-l) in 100-200 In a lp PrePaYammt equiv em amwms e oxymilliliters of isopropanol was added 0.l mole of NaOH (powalkylprienolor alcohol and i lde were lsdered or pellets) and the mixture stirredfor one-half hour to solved m when? or Xylene (about 750 Hummers ofmhiene or form the sodium salt of the mercaptan. The chlorinatedethoxxylene/0'1 equwaleni .ethoxylamd alkylPhenol) with ylatednonylphenol or alcohol (dispersed in 25-50 milliliters gramp-toluenesulfonlc acld for each 0.1 equlvalent of ethoxyof isopropanol)was then added dropwise to the mercaptan lated alkylphenol or alcohol.The solution was heated to reflux Salt over a period of 30 minutes andthe resulting mixture and the solvent-water azeotrope was graduallyremoved. The heaed to reflux (about C) and refluxed for from 2 to 4reactor temperature rose from l0 160 when no hours. The resultingreaction products were filtered to remove W 3' f was the solid NaCl andthe filtrate subjected to distillation under neutrahzed with a has:exchange resm or BMOH) reduced pressure to remove the isopropanolsolvent. Reactered and the solvent removed from the final sulfideproduct 35 tams producw, amounts and yields are recorded and at reducedpressure. marized in table L Table I has been broken into two sectionsfor a systematic 0 B GENERAL MET" D 7% presentation of the experlmentaldata. Table ll shows the com- Oxidation of the sulfide (produced byGeneral Method A or pounds and their properties in the same numericalorder.

TABLE I Reactants Amounts of reactants 1%: I II I II l 0 770 am 42.8rams 1 o.H..-oomcmo ,.n s cmcm H j 2 (ogtlmg ey (O 35gmole) 2 Same asabove oI1@-0HQ-3s-omom0H 00 grams 12.06 grams (.09 male)- (.00 mole)- CH OCH2CH20 2uCHzCH2 3 a m H202 48.64 grams 9.07 grams, 30

""" f (.04 mole). pgrfeeglgs a S \CHz/ aCHs H2020 mole).

I SCH CHoOH 220 rams 38 rams 4 CnH 90 CHzCHz0/20H CH3 \CHz/ 1 2 ((52mole) (8 018) H OH OH 18.806 rams 5 same as above 01 Q C 2 2 003%. (0.1rn0le).

f 198 ams 18.806 grams 6 CBHIB QOTCHZCHZOZH Same above 5; l (0.1 mole)-398 rams 12.4 rams 7 Same asabove S \CHQCIROH 2 mole).

55.0 rams 8.72 grams a CBHIQ-OTCHKJHQOZ-CHHJHZCI cwmlsn (3% qpzwww We):

WIMfi H O 39.28 rams 9.07 grams 9 GoH1o0-(OHCHzO/"CHzCHzS CHzCHzCHa 2 a(.O4 mo1e)- (08111019)- l- SCH OH OH 88 rams 18.8 grams lo"... cnzmQ-ocHtcH.o H o t 2 (6mm 9 m TABLE lrcyn jni ed Fx Reactants Amounts ofreactants No. I II I II 11 f H20; 35 grams 3.117 grams, 30

CH1e OCHzCH;OOHsCHz-SCwHn (0.0275 mole). percent in (.0275 mole 13..Same as above 80.6 grams 0.68 grams -CH2CII2SII (0.07 mole). (0.07mole).

14.. 176.0 grams 12.2 grams CnHn OCH CH O H HOG-H 2 2 2CHzS (0.2 mole).(0.1 mole). /us

15.. O 88.0 rams 15.96 rams I:COHnO%CHzCH:O}-CHzCHz l-S CH g 0 0H 0.1mole). 0.2% mole).

16 f (H0 CH2CH2 -B 125.2 grams 12.2 grams o.H1. OCH:CH:O 0.2 mole). 0.1mole).

17 f "1 0 131.8 grams 15.96 grams CnHm- OTCH2CHzO/CH2CH2T CH g 0 on (0.1male) (0.21 mole).

18..-- f H202 48.3 grams 5.63 grams of [CgH -OCHaCHzO-CH2CH2 (0.05mole). 30% H:

\ j 10 J2 in Water.

19 f CHaCHzCHzSCHzCHzOH 96.08 grams 13.02 grams CoHln- OCHzCH20-H (0.11mole). (0.11 mole).

A. 20 C1zHzaO- OHzOH2O -H n-CaHnSCHaCHzOH 148 grams 7 19 grams jzs (0.1mole). (0.1 mole). 21... Ol2 'l6 2533O- 'CH2CH20 CHQOHZCI 14 36.0 grams14 6.21 grams A omen (0.05 mole). 0.05 mole).

22m.- 5(CH20H0HMCH3 7 110 grams II 7.5 grams oH1o O-(CH:CH:O/H (0.1mole). (0.05 mole).

TABLE I.SEOTION 2 Method Yield Example of prep- (percent Physicalproperties Number aration of theory) Compound prepared 01 compound 1 A83 whitish waxy solid.

[emu-Q0%0H,0H,0}-cmcm3 s 20 f.

2 A 79. 6 f f Clear amber solid at 09H; O-\CH CH;O/-CH;CH S TCHz CHgroom temperature.

3 C 88.9 0 0 Dark yellow liquid.

CBHIO' O- CHzOI zO-CII:CH:S \CI'IZ'OI13 4 A White waxy solid o.H..--0 CHCH O CH;CH1S-Cl OH :0 1

5 A 86. 5 f Amber waxy solid.

C9H10 O--CHzC-HzO-zo-CHzCHz-S -Cl 6 A 89. 3 f Light brown waxy solid.

CoH|n O\CHgCHzO7m-CIIzGlIrS- C1 7 A 86. 6 f '1 Tan waxy solid. CoH19O(CHzCH:O/40CH CHz-JS 8 D 70. 3 f Light tan waxy sllid.

CaH1s O- CHzOH 0/-CH CH SC H l 9 C 76.0 f Light green liquid. C91I1gOTCH CH OTCIBCII S-C1I C11 C1-i 10 A 88.8 f Medium dark brown CnH -0\CHCH,07ClI C1I -S- Cl liquid.

I y; SECTION 2-Continued l Method Yield Example of prep- (percentPhysical properties Number aration of theory) Compound prepared ofcompound 11 h 67.8 CnHn-0{CH2CH2O}CH2CH2SCmH2i Amber waxy solid.

12 b 00.0 onm--o-omcmo -crncm-s-om-Q Light gray solid.

13 D 87. 4 CtHwO-CH2CH20 CH2CHz- B -CH:QHz- Gray waxy solld.

lfl

14 A 86. 6 D [c.ri..-o-cmom0}c alongs 15... C 66. 9 0 Dark amber liquid.

CnH1r- OC H CII O -OH C H S ill .12

16 r. A 03.4 f Dark brown liquid.

CeHrn- O(CHgCHgO--CH1C 1j-s "I 82.6 COHl0- OTCHSCHIOTCHSCHZT o z 18 B 0Amber viscous liquid.

'l 50.0 [C9111 0\CH2CH20TCH2CHTS\ ii 2 19 A f Amber liquid. 88. 8 CoHtOTCH2CH1OCH2CHa-SCHrCHaCHs W Mm v M "Q7 M wawm ll! 20 A 85. 0 Cl2H25 o CH2CI{20) C H2O Hz-S-CgHn Brown, viscous liquid.

21 D 90.0 Crz-ruHzs 0 CH2CHzO -CH CH2S'-CHz- D0- 22 A Do.

Table II summarizes the useful properties of the compounds of theinvention. giving the surfactant profiles of the compounds and severalspecialized biological utilities. The surface tension and interfacialtension (water-mineral oil) of a 0.1 percent by weight solution of theindicated compound in distilled water is given. In addition, the initialfoam height and the height after 5 minutes was measured. This foamheight test illustrates the low foaming characteristics of the class ofcompounds prepared according to the present invention. The wetting timeshows that the sulfur-containing compounds of the invention retainexcellent emulsifying and dispersive power. even though the foamingproperties have been reduced.

The biological results reported in table II were obtained as follows:

Cercospora belicula Candida albicans Trichophylon menlagrophyles Theseorganisms were seeded over the surface of nutrient agar which had beenpoured into large flat pans. Droplets of solutions of the chemicalcompounds shown in table II were spaced over the surface of the agar andcleared zgnes gf in; hibition observed after a suitable incubationperiod. The concentration given in table II shows the lowestconcentration of the compound which gives a cleared zone. The compoundswere dissolved in water or isopropanol prior to seeding.

Powdery (bean) mildew (Erysphe polygom' The host bean; plant is sprayedwith an aqueous dispersion Lone Star tick (Amblyomma americanum Nymphsof the Lone Star tick were dipped into an acetone solution of thecompounds indicated in table II. The impregnated ticks were then placedon absorbent paper to remove the excess solution and to dry before beingplaced into vials. Readings are taken the 4th day after treatment. Afigure of indicates a 100 percent kill at the concentration given.

Mouse Pinworrns Medicated diets containing the compounds indicated intable [I were fed to mice naturally infected with pinworms. Necropsyfindings at the termination of the tests (7 days) were the basis of thetest evaluation. Activity against pinworms is interpreted as 100 percentor is of no calculable effect.

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a. R is an alkyl group of from 10 to l8 carbon atoms, or an alkylphenylgroup of 14-24 carbon atoms, R, and 1 being the same on both Sides of--A- b. Each n is an integer offrom 5 t 50, l0 7. The compound of claim1 wherein R is an alkyl group of c. A is a divalent ulf 5 12 to 16carbon atoms, n is 15 to 40, A is --S- and R is an d. R is hydrogen oran alkyl group of from one to four car- 1 alkyl group of 12 to 16 carbonatomsbon atom and E 8. The compound of claim 7 wherein R is an alkylgroup of 0 is an alkyl group of from one to 12 carbon atoms, an lh'eeeigh carbon atomsaryl hydrocarbon of no more than [0 carbon atoms, a i15 A compound of formula halophenyl group, a halophenethyl group, ahalobenzyl i group, where, in said halophenyl, halophenethyl and H22O--CHCH;S-R

halobenzyl groups, the halogen is C1 or Br, or a group of I n 1'2 theformula 20 wherlelin alk] ff 10 1a b a. is an y group 0 rom to car onatoms, or an R o \OHZCmO CIJHOHF alkylphenyl group of 14-24 carbonatoms,

b. n is an integer of from 5 to 50,

h i R, Rl and n are as defined above: c. R is hydrogen or an alkyl groupof from one to four car- 2. The com und of claim 1 wherein R s alk l h l'25 atomsiand r 'b of l 4 g carbon atoms. 1 an y p my I d. R, is analkyl group of from three to eight carbon atoms.

3. The compound of claim 1 wherein R is a straight chain a v. V alkylgroup of l 2 to lo carbon atoms.

2. The compound of claim 1 wherein R is an alkylphenyl group of 14 to 18carbon atoms.
 3. The compound of claim 1 wherein R is a straight chainalkyl group of 12 to 16 carbon atoms.
 4. The compound of claim 1 whereinn is 15 to
 40. 5. The compound of claim 1 wherein Ro is a halophenylgroup.
 6. The compound of claim 1 wherein R0 is R, n and R1 being thesame on both sides of -A-.
 7. The compound of claim 1 wherein R is analkyl group of 12 to 16 carbon atoms, n is 15 to 40, A is -S- and Ro isan alkyl group of 12 to 16 carbon atoms.
 8. The compound of claim 7wherein Ro is an alkyl group of three to eight carbon atoms.
 9. Acompound of the formula wherein a. R is an alkyl group of from 10 to 18carbon atoms, or an alkylphenyl group of 14- 24 carbon atoms, b. n is aninteger of from five to 50, c. R1 is hydrogen or an alkyl group of fromone to four carbon atoms, and d. Ro is an alkyl group of from three toeight carbon atoms.